Treatment of hydrocarbons



March 7, 1933. w. R. HOWARD TREATMENT OF HYDROCARBONS K Original FiledFeb. 2l, 1927 111m ww. -I Nw uw In... HH- @N .uh w A l- K \w\ fr 1 1 nN1 i im N rf top of the deph egmator line 10,

Patented Mar. 7, 19,33

UNITED s'ijATEs PATENT Aori-ICE WILLIAM R. HKDWAXD, .OF WASHINGTON,DISTRICT F COLUMBIA, ASSIGNOR TO UNI- vEnsAL oLYPRoDUc'rs COMPANY,soU'rH DAKOTA TREATMENT 0F HYDROCARBONS Application led Februaryf21,1927, Serial No. 169,774. Renewed February 4, 1931'.

The present invention relates to improvements in the art of conversionof heavier hydrocarbons into lighter hydrocarbons', but moreparticularly to a process wherein the heavier ends or residue are soprocessed as to remain in a liquid form and yet yield a greater amountof lighter hydrocarbons, such as asoline and the like. i'

n the cracking of hydrocarbon oils of the present time, it has beenexperienced that a crude oil of 209'Bauni gravity may be converted into(i-75% more or less, of light distillates, such as gasoline, andtheremainder into solid coke,qex'cept for a small percentage of gas. Ithas also beenexperienced that this same crude may be converted into'I5-85% more or less, of a similar light distillate, 5-10,`/(, moreorless, into heavyr residual oil, and the' balance into solid coke, withthe exception of the same small percentage of gas.

`One of the objects of thepresent invention -is to convert substantiallythe entire crude into liquid products wherein the overhead lightdistillates comprisesthe greater percent, and the remaining residuumwisa liquid product having commercalvalue as fuel oil free from coke.` j yOther objects and advantages will more completely `apparent froin vthe.following description.

in the drawing, ai@ Si'ngieiigure is a Side elevationall view showingdiagrammatically apparatus for carrying out the invention.

Referring more in-detail to the drawing, 1 represents a feed pump forforcing vthe ch'arg ing stock through line 2 controlled by valve 2' intocracking tube'3 mounted in furnace 4. Line' 5 is a transferline'from-the cracking tube controlled byvalve 5", into expansionchamber'G;v Erom the top of expansion chamber 6, a vapor line7,.provided with valve 8, leadsto the de hlegmator 9 andv from therovided with valve 11, ,leads to vwater coo ed.'con denser 12,continuing through rundown line 13, controlled by Avalve 14, int0receiver 15. Receiver ma he provided with a gasontlet at the top. intheform of-pipe 16, controlled by valve 17, and near the bottom thereofpipe 18, controlled by valve 19,- for the vwithdrawal lof the condenserliquids'. Line 20, controlled by valve 21, is za bottom drawof forreceiver 15.

From the side of expansion chamber 6 at different levels are outlet.pipes 22, 23 'and 24, controlled by valves 25, 2G and 27, respectively,running to a common line 28, which continues into mixing chamber 29. Atthe bottom of expansion chamber 6 an additional residuum drawofi' 30 maybe provided, which enters line 28 through valve 31; this drawoff 30 alsohas an outlet 92, controlled by valve l33, for withdrawing,rcsiduunifrom the system toa supply tankl (not shown).

To the bottom of dephlegmator 9 maybe connected the reflux leg 34 whichmay com 0F CHICAGO, ILLINOIS, A CORPORATION OF I munic'ate withmixing'chainber 29. Mixing Y chamber 29 may be providedwith a stirringmechanism 35-and means for revolving same i at 36. vF rom the top ofmixing chamber 29 a livered through-line 41, through heat ex-v changer42, here shown 'located in the top of dephlegmator 9 and on into mixingchamber 29. This charging line 4l may be provided with valves 43 and 44and by-pass line 45 so that the charging stock may be fed directly intothe top of dephlegniator 9 through nozzle 4G and reach mixing Achamber29 through icliux leg 34.-

It isv z. well known fact today that-in the lcracking of. petroleum oilscertain disadvantagesa'aI .experiencedin -piissin'gfoil to `be crackedonce through the crackinghzone with:2 out the return ofthe refluxcondensate in that when ani' substantial 'crackingis produced thecrackingtubes quicklyr till up with a heavy` carbon-like sulistancelandcoke and even if the charging stock is continuously supplied with arrtlnx condensate and'passcd through the cracking zonein order to obtaina large yield of lighter distillates, this coke or cokelike material isnecessarily deposited in the expansion chamber.

and is picked up by pump 1, and through line 2 is sent through crackingtubes 3 where it is heated to the desired cracking temperature, which,in this process, need vnot be as high as 850 or 900 F., but whereinatemperature of 750 or 809 F. will produce the desired results. Theheated charging stock is then discharged into expansion chamber 6 wherea separation or reaction takes place, the lighter vapors `going throughvvapor line 7 into dephlegmator 9 and the heavier portion going outthrough line 30 with valve 33 closed, and into line 28, and then intomixing chamber 29. `As the vapors from the vapor line reach dephlegmator9 they are separated into lighter vapors which pass out through vaporline 10 and on into receiver 15, after being condensed in condenser 12,and into heavier f1 actions which drop tothe bottom as redux condensate,being withdrawn through line 34 and passed to mixing chamber 29.

As the process continues the residuum from expansion chamber 6, theredux from dephlegmator 9, and the charging stock passed through line 41all come together in mixing chamber 29 where the'y may or maynot begiven mechanical agitation by. means of stirrer 35. As pump 11 continuesto pick up thisvmaterial and circulate it through cracking tubes 3, thetemperature dually increases and it is so treatedun'ti vapors having adesired end boiling point are coming from the' top of dephlegmator 9. lAs the process progresses' and the liquid level in the expansion chamber6 rises, the residuum may be drawn od and into .mixing chamber 29through either of valves 25', 26 or 27 and into mixing chamber by vmeanso'f line 28.

If this process continues as so far described, certain results may beobtained, but in a much shorter period of time the cracking tubes 3 ,mayclog up with c oke and the accumulation of coke 1n expansion chamber'6may prevent the withdrawal of residuum and constitute the end of a run.To overcome this objection, pump 39 is started anda portion of the oilin the mixing chamber 29, which is at a tem perature far below that ofthe oil in the transfer line 5 is fed into expansion chamber 6 and comesin contact with the residuum or heavier ends resulting from theseparation oftheoil in the expansion chamber and so retgulates thenature, viscosity, and character o this resid uum as to keep it inliquid form and continually allow same or a portion of same to dow 5back to mixing chamber 29 whereV it is mixed with redux and chargingstock for further cracking in coil 3.

As this residuum becomes heavier a portion of same may be withdrawnthrough line 30 at the bottom of expansion chamber 6 and by regulatingvalves 31 and 33 may-be drawn otf through line 32 into a fuel oilstorage tank (not shown).

By operating the process as above described, the oil to be treated canbe subjected an increased number of times to milder cracking conditionsas it passes through cracking tubes 3 and to a' greater agitation in thering or cycle, which .prevents the accumulation of undesirable coke andalso allows a greater yield of lighter distillates or gasoline withoutforming any substantial amount of coke and forming a residuum salable ascommercial fuel oil. A

The process may be operated with predetermined superatmosphericpressures from three to several hundred pounds on the cracking tube 3,expansion chamber 6, dephlegmator 9, and receiver 15 by the manipulationof valves 11, 14 and 17, or differential pressures may be maintained.

I claim as my inventi'on:

1. A process of hydrocarbon oil conversion comprising subjecting oil tocracking conditions of temperature and superatmospheric pressure in aheating zone to cause substantial vaporization, passing the heated oilto a vapor separating zone and there separat-l ing the vapors,subjecting the vapors to tedux condensation, separately condensing andcollecting the uncondensed vapors subsequent to redux condensation,removing from the vapor separating zone regulated portions ofnon-vaporized residue and passing same to an enlarged mixing zonewherein a substantial body accumulates, removing from the reduxcondensing zone regulated portions of redux condensate and passing sameto said mixing zone wherein a substantial body thereof accumulates andmixes with said substantial body of non-vaporized residue, and removingfrom said mixing zone regulated portions of said mixture and directingsame directly and without passage through said heating zone to said'vapor separating zone where said mixture mixes with the non-vaporizedresidue accumulated in said vapor separating zone.

2. A process of hydrocarbon oil conversion comprising subjecting oil tocracking conditions of temperature and'superatmospheric pressure in aheating zone to cause substantial vaporization, passing the heated oilto a vapor separating zone and there separating the vapors, subjectingthe vapors to rcdux condensation, separately condensing and collectingthe uncondensed vapors subsequent to redux condensation, removing fromthe vapor separating zone regulated portions of` non-vaporized residueand passing same to a mixing zone, removing from the' reflux condensin gzone regulated portions of reflux condensate and passing same to saidmixing zone Where it mixes with said non-vaporized residue, and removingfrom said mixing zone regulated portions of said mixture and passingsame directly and without passage through said heating zone to saidvapor separating zone at a point removed from the heated oilintroduction where said mixture mixes with the non-vaporized residueaccumulated in said vapor separating zone and continuously withdrawingfrom said vapor separating zone regulated portions of the heavynon-vaporized residue and isolating same from the system.

8. A process of hydrocarbon oil conversion comprising subjecting oil tocracking conditions of temperature and superatmospheric pressure in aheating zone to cause substantial vaporization, passing the heated oilto a vapor separating zone and there separating the vapors, subjectingsame to reflux condensation, separately condensing and collecting theuncondensed vapor subsequent to reflux condensation, removing from thevapor separating zone regulated portions of non-vaporized residue andpassing same to a mixing zone, removing from the reflux condensing zoneregulated portions of reflux condensate and passing same to said mixingzone Where it mixes with said iion-vaporized residue, removing fiom saidmixing zone regulated portions of said mixture and directing same to theheating Zone for retreatiiient, removing additional portions of saidmixture from said mixing zone and directing the same directly andwithout application of additional heat into said separating zone priorto admixture with the heated oil supplied thereto.

4. A process of hydrocarbon o'il conversion comprising subjecting oil tocracking conditions of temperature and superatmospheric pressure in aheating zone to cause substantial vaporization, passing the heated oilto a vapor separating zone and there separating the vapors, subjectingthe vapors to reflux condensation, separately condensing and collectingthe uncondensed vapors subseguent to reiiux condensation, removing romthe vapor separating zone regulated portions of non-vaporized residueand passing same to a mixing zone, `removing from the refiux condensingzone regulated portions of reflux condensate and passing same tol saidmixing zone where it mixes with said nonvaporized residue, and removingfrom said mixing zone re lated portions of said mixture and directingsame to said vapor separating zone where said mixture mixes with thenon-vaporized residue accumulated in said vapor separating zone, insimultaneously and separately removing from said mixing zone controlledquantities of said mixture and directing same to said heating zone.

5. A process of hydrocarbon oil conversion comprising subjecting oil tocracking conditions of tem erature and superatmospheric pressure in a'eating zone to cause substantial vaporization, passing the heated oilto a vapor separating zone and there separating the vapors, subjectingthe vapors to reflux condensation, separately condensing and collectithe uncondensed vapors subsequent to re ux condensation, removing fromthe vapor separating zone regulated portions of nonvaporized residue andassing same to a mixing zone, removing rom the reiux condensing zoneregulated portions of reflux condensate and assing same to said mixingzone where it mixes with said non-vaporized residue, and removing fromsaid mixing zone regulated portions of said mixture and directing sameto said vapor separating zone where said mixture mixes with thenonvaporized residue accumulated in said vapor separating zone, insimultaneously and separately removing from said mixing zone controlledquantities of said mixture and directing same to said heating zone, andmixing with the latter controlled quantities of fresh charging stock.

6. A process of hydrocarbon oil conversion comprising subjecting oil tocracking conditions of temperature and superatmospheric pressure in aheating zone to cause substantial vaporization, passing the heated oilto a vapor separating zone and there separating the vapors, subjectingthe vapors to reflux condensation, separately condensing andcollectingi-l the uncondensed vapors subsequent to reflux condensation,removing from the vapor separating zone regulated portions ofnon-vaporized residue and passing same to a mixing zone, removing fromthe reflux condensing zone regulated portions of reflux condensate andpassing same to said mixing zone where it mixes with said non-vaporizedresidue, and removing from said mixing zone regulated portions of saidmixture and directing same to said vapor separating zone where ysaidmixture mixes with the nonvaporized residue accumulated in said vaporseparating zone, the portions of said mixture from the mixing zone beingintroduced to the vapor separating zone at a lower tem` perature thanthe temperature of the hydrocarbons within the vapor separating zone.

7. A process of hydrocarbon oil conversion comprising subjecting oil tocracking conditions of temperature and superatmospheric pressure in aheating zone -to cause substantial vaporization, passing the heated oilto a vapor separating zone and there separating the vapors, subjectingsame to reux condensation, separately condensing and collecting theuncondensed vapors subsequent to reux condensation, removing from thevapor separating zone regulated portions of non-vaporized residue andpassing same to a mixing zone, removing from the reflux condensing zoneregulated portions of reflux condensate and passing same to said mixingzone where it mixes with said non-vaporized residue, and removing fromsaid mixing zone regulated portions of said mixture and directing sameto said vapor separating zone where said mixture mixes with thenon-vaporized residue accumulated in said vapor se arating zonereturning other portions o said mixture to said heating zone,simultaneously removing from the mixing zone any released vapors andpassing same to said dephlegmating zone and maintaining a lower pressurein said mixing zone than is maintained in said separating zone.

8. A process of hydrocarbon oilconversion which consists in passing theoil through a heating coil wherein it is heated to a crackingtemperature under superatmospheric pressure, discharging the heated oilkinto an enlarged zone of reaction wherein vapors are evolved andseparate from unvaporized oil, taking olf the vapors and subjecting themto dephlegmation, passing the refiux condensate to a mixing zone,passing unvaporized oil from said zone of reaction to said mixing zone,returning vapors from said mixing zone to the dephlegmation step,removing regulated portions of said mixture from said mixing zone andintroducing said portions to said zone of reaction apart from thedischarge of heated oil thereinto.

9. `A process of hydrocarbon oil conversion which consists in passingthe oil throuvh a heating coil wherein it is heated to a craclliingtemperature under superatinospheric pressure, discharging the heated oilinto an enlarged zone of reaction wherein vapors are evolved andseparate from unvaporized oil, taking oi the vapors and subjecting themto dephlegmation, passing the reflux condensate to a mixing zone,passing unvaporized oil from said zone of reaction to said mixing zone,passing charging oil for the process in heat interchange with the vaporsundergoing dephlegmation and then passing such char g oil to the mixingzone, removing regu ated portions of said mixture from said mixing zoneand introducing said portions to said zone of reaction apart fromthedischarge of heated oil thereinto.

10. A rocess of hydrocarbon oil conversion which consists in passing theoil throu h a heating coil wherein it is heated to a crac ingtemperature under superatmospheric pressure, discharging the heated oilinto an enlarged zone of reaction wherein vapors are evolved andseparate from unvaporized oil, takin oi the vaporsand subjecting them todep legmation, passing the reflux condensate to a zone, passing theunvaporized oil from said zone of reaction to said mixing zone,subjecting the contents of said mixing zone to agitation, removingregulated portions of said mixture from said mixing zone and introducingsaid portions to said zone of reaction apart from the discharge ofheated oil thereinto.

11. A process for cracking hydrocarbon oil comprising passing the oilthrough a heating coil and thence to the first of serially connectedenlar ed chambers, delivering liquid oil fromthe to the second enlargedchamber, taking off vapors from the second enlarged chamber, paing saidvapors to a reflux condenser, introducing charging oil for the processand reflux condensate from said reflux condenser to said second enlargedchamber, maintaining a local cyclic circulation through said enlargedchambers by withdrawing oil from the second chamber and returning itdirectly to the first chamber and maintaining a second cycliccirculation through said heating coil and chambers by withdrawingadditional oil from said second chamber and supplying the same to saidheating coil.

12. A process for cracking hydrocarbon oil comprising passing the oilthrough a heating coil and thence to the first of serially connectedenlarged chambers, taking off vapors therefrom, delivering liquid oilfrom the first to the second enlarged chamber, taking olf vapors fromthe second enlarged chamber, passing said vapors from both chambers toa. reflux condenser, introducing chargin oil for the process and refluxcondensate rom said reflux condenser to said second enlarged chamber,maintaining a local cyclic circulation through said enlarged chambers bywithdrawing oil from the second chamber and returning it directly to thefirst chamber and maintaining a second cyclic circulation through saidheating coil and chambers by Withdrawin additional oil from said secondchamber an supplying the same to said heating coil.

WILLIAM R. HOWARD.

